U.S. patent number 11,090,910 [Application Number 16/619,763] was granted by the patent office on 2021-08-17 for metal pattern film and manufacturing method therefor.
This patent grant is currently assigned to LG CHEM, LTD.. The grantee listed for this patent is LG CHEM, LTD.. Invention is credited to Song Ho Jang, Kiseok Lee, Seung Heon Lee, Jiehyun Seong.
United States Patent |
11,090,910 |
Lee , et al. |
August 17, 2021 |
Metal pattern film and manufacturing method therefor
Abstract
A metal pattern film including a substrate; a first adhesion
promoting layer provided on a first surface of the substrate; a
second adhesion promoting layer provided on a second surface of the
substrate, which is opposite to the first surface of the substrate;
a metal pattern provided on a surface of the first adhesion
promoting layer opposite to a surface of the first adhesion
promoting layer adjoining the substrate; a first adhesive layer
provided on a surface of the metal pattern opposite to the first
adhesion promoting layer so as to cover the metal pattern; and a
second adhesive layer provided on a surface of the second adhesion
promoting layer opposite to a surface of the second adhesion
promoting layer adjoining the substrate. Each of the first adhesion
promoting layer and the second adhesion promoting layer includes an
inorganic oxide. A method for preparing a metal pattern film.
Inventors: |
Lee; Kiseok (Daejeon,
KR), Jang; Song Ho (Daejeon, KR), Seong;
Jiehyun (Daejeon, KR), Lee; Seung Heon (Daejeon,
KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
LG CHEM, LTD. |
Seoul |
N/A |
KR |
|
|
Assignee: |
LG CHEM, LTD. (Seoul,
KR)
|
Family
ID: |
1000005747973 |
Appl.
No.: |
16/619,763 |
Filed: |
March 27, 2018 |
PCT
Filed: |
March 27, 2018 |
PCT No.: |
PCT/KR2018/003607 |
371(c)(1),(2),(4) Date: |
December 05, 2019 |
PCT
Pub. No.: |
WO2018/225938 |
PCT
Pub. Date: |
December 13, 2018 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
|
US 20200101700 A1 |
Apr 2, 2020 |
|
Foreign Application Priority Data
|
|
|
|
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Jun 9, 2017 [KR] |
|
|
10-2017-0072675 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09J
129/04 (20130101); C23C 14/30 (20130101); C23F
1/02 (20130101); C09J 167/02 (20130101); B32B
17/10183 (20130101); C23C 14/08 (20130101); B32B
17/1022 (20130101); B32B 17/10779 (20130101); B32B
17/10018 (20130101); C23C 14/34 (20130101); B32B
7/12 (20130101); Y10T 428/24917 (20150115) |
Current International
Class: |
B32B
3/00 (20060101); C23F 1/02 (20060101); C23C
14/34 (20060101); C23C 14/08 (20060101); C23C
14/30 (20060101); C09J 167/02 (20060101); C09J
129/04 (20060101); B32B 7/12 (20060101); B32B
17/10 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2016120894 |
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10-2012-0012568 |
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Feb 2012 |
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10-20140147719 |
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Dec 2014 |
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KR |
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101549987 |
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Sep 2015 |
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KR |
|
10-2015-0116767 |
|
Oct 2015 |
|
KR |
|
10-1718780 |
|
Mar 2017 |
|
KR |
|
Primary Examiner: Dumbris; Seth
Attorney, Agent or Firm: Dentons US LLP
Claims
The invention claimed is:
1. A metal pattern film comprising: a substrate; a first adhesion
promoting layer provided on an entirety of a first surface of the
substrate; a second adhesion promoting layer provided on an
entirety of a second surface of the substrate which is opposite to
the first surface of the substrate; a metal pattern provided on a
surface of the first adhesion promoting layer opposite to the
surface of the first adhesion promoting layer adjoining the
substrate; a first adhesive layer provided on a surface of the
metal pattern opposite to the first adhesion promoting layer,
wherein the first adhesive layer covers the metal pattern; and a
second adhesive layer provided on a surface of the second adhesion
layer opposite to the surface of the second adhesion layer
adjoining the substrate, wherein each of the first adhesion
promoting layer and the second adhesion promoting layer comprises
an inorganic oxide, wherein each of the first and second adhesion
promoting layers has a thickness of greater than or equal to 0.1 nm
and less than or equal to 20 nm.
2. The metal pattern film of claim 1, wherein each of the first and
second adhesion promoting layers comprises one or more selected
from the group consisting of niobium oxide, aluminum oxide, silicon
oxide, zinc oxide, tin oxide, zirconium oxide and indium tin
oxide.
3. The metal pattern film of claim 1, wherein the metal pattern
comprises one or more selected from the group consisting of
aluminum, copper, nickel, chromium, gold, silver and platinum.
4. The metal pattern film of claim 1, wherein the metal pattern has
a line height of 10 .mu.m or less.
5. The metal pattern film of claim 1, wherein the metal pattern has
a line height deviation of 20% or less.
6. The metal pattern film of claim 1, wherein each of the first and
second adhesive layers comprises polyvinyl butyral (PVB), ethylene
vinyl acetate (EVA), polyurethane (PU) or polyolefin (PO).
7. The metal pattern film of claim 1, wherein each of the first and
second adhesive layers is a polyvinyl butyral (PVB) layer.
8. The metal pattern film of claim 1, wherein each of the first and
second adhesive layers has a thickness of greater than or equal to
1 .mu.m and less than or equal to 1000 .mu.m.
9. Laminated glass comprising the metal pattern film of claim
1.
10. A method for preparing the metal pattern film of claim 1, the
method comprising: preparing a substrate; forming a first adhesion
promoting layer on an entirety of a first surface of the substrate;
forming a second adhesion promoting layer on an entirety of a
second surface of the substrate, which is opposite to the first
surface of the substrate; forming a metal pattern on a surface of
the first adhesion promoting layer opposite to a surface of the
first adhesion promoting layer adjoining the substrate; forming a
first adhesive layer on a surface of the metal pattern opposite to
the first adhesion promoting layer so as to cover the metal
pattern; and forming a second adhesive layer on a surface of the
second adhesive promoting layer opposite to a surface of the second
adhesive promoting layer adjoining the substrate, wherein each of
the first adhesion promoting layer and the second adhesion
promoting layer comprises an inorganic oxide, wherein each of the
first and second adhesion promoting layers has a thickness of
greater than or equal to 0.1 nm and less than or equal to 20
nm.
11. The method for preparing the metal pattern film of claim 10,
wherein the forming of a metal pattern comprises forming a metal
layer; and patterning the metal layer.
12. The method for preparing the metal pattern film of claim 11,
wherein patterning the metal layer comprises forming an etching
resist pattern on the metal layer, and removing the metal layer
that is not covered by the etching resist pattern.
13. The method for preparing the metal pattern film of claim 10,
further comprising peeling off the first adhesive layer from the
metal pattern film.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage of International Application
No. PCT/KR2018/003607 filed Mar. 27, 2018, and claims priority to
and the benefits of Korean Patent Application No. 10-2017-0072675,
filed with the Korean Intellectual Property Office on Jun. 9, 2017,
the entire contents of which are incorporated herein by
reference.
TECHNICAL FIELD
The present application provides a metal pattern film comprising an
adhesion promoting layer and a method for preparing the same.
BACKGROUND
When manufacturing functional laminated glass used for automobiles
or construction, polyvinyl butyral (PVB) is generally used as an
adhesive. Laminated glass provided with special function is
manufactured using a thermocompression process by inserting a
polyvinyl butyral (PVB)-laminated functional film between two
sheets of glass.
In order to manufacture film-inserted functional laminated glass,
adhesive strength between the polyvinyl butyral (PVB) and the
functional film needs to be at a certain level or higher, and
peel-off needs to be possible in order to allow reprocessing.
When peeling off an existing polyvinyl butyral (PVB)-laminated
polyvinyl butyral (PVB)/functional film, a stick-slip phenomenon
occurs, which leads to a disadvantage such that wrinkles and stains
remain making reuse impossible.
A PET film is used as a functional film generally used in the art,
and the PET film goes through a stick-slip phenomenon in the
peel-off accompanying vibrations when peeling off between surfaces,
and reuse is impossible since wrinkles and stains remain.
Accordingly, in manufacturing functional laminated glass, a metal
pattern film resolving a stick-slip phenomenon and thereby making
reprocessing possible with no wrinkles and stains remaining.
SUMMARY
The present application is directed to providing a metal pattern
film enhancing adhesive strength with an adhesive layer and
resolving a stick-slip phenomenon when peeled off by forming an
ultra-thin adhesion promoting layer on a surface of a
substrate.
One embodiment of the present application provides a metal pattern
film comprising a substrate; a first adhesion promoting layer and a
second adhesion promoting layer each provided on both surfaces of
the substrate; a metal pattern provided on a surface opposite to
the surface adjoining the substrate of the first adhesion promoting
layer; a first adhesive layer provided on the surface provided with
the metal pattern of the first adhesion promoting layer so as to
cover the metal pattern; and a second adhesive layer provided on a
surface opposite to the surface adjoining the substrate of the
second adhesion promoting layer, wherein the first adhesion
promoting layer and the second adhesion promoting layer comprise an
inorganic oxide.
Another embodiment of the present application provides laminated
glass comprising the metal pattern film according to one embodiment
of the present application.
Still another embodiment of the present application provides a
method for preparing a metal pattern film comprising preparing a
substrate; forming a first adhesion promoting layer and a second
adhesion promoting layer each on both surfaces of the substrate;
forming a metal pattern on a surface opposite to the surface
adjoining the substrate of the first adhesion promoting layer by
patterning the metal pattern; forming a first adhesive layer on the
surface provided with the metal pattern of the first adhesion
promoting layer so as to cover the metal pattern; and forming a
second adhesive layer on a surface opposite to the surface
adjoining the substrate of the second adhesion promoting layer,
wherein the first adhesion promoting layer and the second adhesion
promoting layer comprise an inorganic oxide.
A metal pattern film according to one embodiment of the present
application forms an ultra-thin inorganic oxide layer on both
surfaces of a substrate to enhance adhesive strength with an
adhesive layer without decreasing transmittance, and by resolving a
stick-slip phenomenon when peeled off, wrinkles and stain formation
are prevented by reducing vibrations when peeling off between
surfaces, which makes reprocessing possible.
In addition, by forming an ultra-thin inorganic oxide layer, the
metal pattern film according to one embodiment of the present
application is effective in enhancing adhesiveness between a
substrate and a pattern layer deposited on the substrate, and may
comprise a function of an adhesion layer of a fabric of a metal
mesh-based transparent conductive film.
Furthermore, by using a nanoscale inorganic oxide layer, the metal
pattern film according to one embodiment of the present application
is transparent and has no changes in the optical properties of the
film, and is thereby useful when manufacturing transparent
functional laminated glass.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a side view illustrating a metal pattern film according
to one embodiment of the present application.
FIG. 2 is a diagram illustrating a peel-off process according to
one embodiment of the present application.
FIG. 3 is a diagram illustrating a method for preparing a metal
pattern according to one embodiment of the present application.
FIG. 4 is a diagram measuring peel strength of a metal pattern film
according to one embodiment of the present application.
REFERENCE NUMERALS
10: Glass 20: First Adhesive Layer 30: Metal Pattern 40: First
Adhesion Promoting Layer 50: Substrate 60: Second Adhesion
Promoting Layer 70: Second Adhesive Layer 80: Glass 90: Metal Layer
100: Etching Resist Pattern
DETAILED DESCRIPTION
Hereinafter, the present specification will be described in more
detail.
Embodiments of the present disclosure will be described in detail
with reference to accompanying drawings so that those skilled in
the art may readily implement the present disclosure.
However, the present disclosure may be embodied in various
different forms, and is not limited to the embodiments described
herein.
A metal pattern film according to one embodiment of the present
application comprises a substrate; a first adhesion promoting layer
and a second adhesion promoting layer each provided on both
surfaces of the substrate; a metal pattern provided on a surface
opposite to the surface adjoining the substrate of the first
adhesion promoting layer; a first adhesive layer provided on the
surface provided with the metal pattern of the first adhesion
promoting layer so as to cover the metal pattern; and a second
adhesive layer provided on a surface opposite to the surface
adjoining the substrate of the second adhesion promoting layer,
wherein the first adhesion promoting layer and the second adhesion
promoting layer comprise an inorganic oxide.
The metal pattern film according to one embodiment of the present
application forms an ultra-thin inorganic oxide layer on both
surfaces of a substrate to enhance adhesive strength with an
adhesive layer without decreasing transmittance, and by resolving a
stick-slip phenomenon when peeled off, wrinkles and stain formation
are prevented by reducing vibrations when peeling off between
surfaces, which makes reprocessing possible, and in addition
thereto, is effective in enhancing adhesiveness between a pattern
and the substrate by forming a nanoscale inorganic oxide layer.
In the present specification, the stick-slip phenomenon means a
friction phenomenon accompanying vibrations when peeling off
between surfaces or a phenomenon decreasing precision through
generating vibrations by causing a motion that is not smooth.
In one embodiment of the present application, the substrate may be
formed with a transparent polymer film.
In one embodiment of the present application, the substrate may be
formed with a PET film, a polycarbonate (PC) film, a polyethylene
naphthalate (PEN) film, but is not limited thereto.
In one embodiment of the present application, the substrate may
have a thickness of greater than or equal to 1 .mu.m and less than
or equal to 200 .mu.m, and preferably greater than or equal to 10
.mu.m and less than or equal to 100 .mu.m.
In one embodiment of the present application, the first and the
second adhesion promoting layers comprise one or more selected from
the group consisting of niobium oxide (Nb.sub.2Ox), aluminum oxide
(Al.sub.2O.sub.3), silicon oxide (SiO.sub.2), zinc oxide (ZnO),
niobium oxide (NbO), tin oxide (SnO), zirconium oxide (ZrO) and
indium tin oxide (ITO).
In the niobium oxide (Nb.sub.2Ox), the range of x is an integer of
1 to 6, and preferably an integer of 1 to 4.
In one embodiment of the present application, the first and the
second adhesion promoting layers may be formed with aluminum oxide
(Al.sub.2O.sub.3).
In another embodiment, the first and the second adhesion promoting
layers may be formed with silicon oxide (SiO.sub.2).
In another embodiment, the first and the second adhesion promoting
layers may be formed with indium tin oxide (ITO).
In another embodiment, the Nb.sub.2Ox layer may be used alone as
the first and the second adhesion promoting layers.
When the Nb.sub.2Ox layer is used alone as the first and the second
adhesion promoting layers, optical properties of the metal pattern
film are most superior.
In another embodiment, an alloy interlayer may be further included
between the first adhesion promoting layer and the surface
adjoining the substrate thereof.
In another embodiment, an alloy interlayer may be further included
between the second adhesion promoting layer and the surface
adjoining the substrate thereof.
In one embodiment of the present application, the alloy interlayer
may have a thickness of greater than or equal to 0.5 nm and less
than or equal to 1.9 nm, and preferably greater than or equal to
0.5 nm and less than or equal to 1.5 nm.
The alloy interlayer having a thickness of 2 nm or greater leads to
performance decline due to a decrease in the visible light
transmittance.
The alloy interlayer may be NiCr, Ni or Cr, but is not limited
thereto.
In the metal pattern film, when using an inorganic oxide layer as
the first and the second adhesion promoting layers, a stick-slip
phenomenon significantly decreases as a result of peel-off
evaluation after thermocompressing the substrate (PET) and
polyvinyl butyral (PVB), and as a result, wrinkles and stains do
not remain making metal pattern film reprocessing possible.
In one embodiment of the present application, the first and the
second adhesion promoting layers each have a thickness of greater
than or equal to 0.1 nm and less than or equal to 30 nm, preferably
greater than or equal to 1 nm and less than or equal to 25 nm, and
more preferably greater than or equal to 1 nm and less than or
equal to 20 nm.
Forming the adhesion promoting layer having a nanoscale thickness
is useful in manufacturing transparent functional laminated glass
since there are no changes in the optical properties of the film,
and without decreasing transmittance, a stick-slip phenomenon may
be resolved when peeled off as well as enhancing adhesive strength
with an adhesive layer.
The metal pattern film according to one embodiment of the present
application has a metal pattern provided on a surface opposite to
the surface adjoining the substrate of the first adhesion promoting
layer.
In one embodiment of the present application, the metal pattern may
comprise one or more selected from the group consisting of
aluminum, copper, nickel, chromium, gold, silver and platinum, and
although copper having excellent electrical conductivity is most
preferred as the metal pattern, the metal pattern is not limited
thereto.
In one embodiment of the present application, the metal pattern may
have a line height of 10 .mu.m or less and preferably 5 .mu.m or
less.
The line height of the metal pattern means a distance from the
surface adjoining the adhesion promoting layer to a surface
opposite thereto.
In one embodiment of the present application, the metal pattern may
have a line height deviation of 20% or less and preferably 5% or
less.
The deviation means, based on an average line height, a percentage
on a difference between the average line height and an individual
line height.
In one embodiment of the present application, the metal pattern may
have a total aperture ratio, that is, a ratio of the substrate area
that is not covered by the metal pattern, of 90% or greater, and
preferably 95% or greater.
In one embodiment of the present application, the metal pattern may
have a line width of 40 .mu.m or less, and specifically 0.1 .mu.m
to 40 .mu.m or less.
In one embodiment of the present application, the metal pattern has
line-to-line spacing of 50 .mu.m to 1000 .mu.m.
In one embodiment of the present application, the first and the
second adhesive layers may comprise polyvinyl butyral (PVB),
ethylene vinyl acetate (EVA), polyurethane (PU) or polyolefin (PO),
and may preferably be a polyvinyl butyral (PVB) layer.
In another embodiment, the first and the second adhesive layers may
each have a thickness of greater than or equal to 1 .mu.m and less
than or equal to 1000 .mu.m, and preferably greater than or equal
to 1 .mu.m and less than or equal to 760 .mu.m.
When each of the first and the second adhesive layers has the
above-mentioned thickness, adhesiveness of the metal pattern film
is enhanced, and particularly when further including laminated
glass, an effect of preventing scattering of debris when the glass
breaks down is obtained.
One embodiment of the present application provides laminated glass
comprising the metal pattern film.
In one embodiment of the present application, the laminated glass
is formed with a constitution further comprising glass on each of a
surface opposite to the surface adjoining the pattern-formed first
adhesion promoting layer of the first adhesive layer and a surface
opposite to the surface adjoining the second adhesion promoting
layer of the second adhesive layer.
The laminated glass may be manufactured through thermocompressing
the temporarily laminated adhesive layer of the metal pattern film
and the glass.
In one embodiment of the present application, as for the lamination
of the first and the second adhesive layers and the glass, the
temporarily laminated adhesive layer is inserted between tempered
glass to manufacture into a sheet unit at a temperature of
140.degree. C. or higher using a thermocompression equipment such
as a vacuum laminator or autoclave.
According to one embodiment of the present application, a primer
layer may be further provided at an interface of the metal pattern
and the substrate.
One embodiment of the present application provides a method for
preparing a metal pattern film comprising preparing a substrate;
forming a first adhesion promoting layer and a second adhesion
promoting layer each on both surfaces of the substrate; forming a
metal pattern on a surface opposite to the surface adjoining the
substrate of the first adhesion promoting layer by patterning the
metal pattern; forming a first adhesive layer on the surface
provided with the metal pattern of the first adhesion promoting
layer so as to cover the metal pattern; and forming a second
adhesive layer on a surface opposite to the surface adjoining the
substrate of the second adhesion promoting layer, wherein the first
adhesion promoting layer and the second adhesion promoting layer
comprise an inorganic oxide.
In the preparation method according to one embodiment of the
present application, the first and the second adhesion promoting
layers may be formed on the substrate by a vapor deposition process
using e-beam sputter equipment, however, the method is not limited
thereto.
In the preparation method according to one embodiment of the
present application, the forming of first and second adhesive
layers on each of the first adhesion promoting layer and the second
adhesion promoting layer may use a process of thermocompression,
solid-state adhesive film lamination or liquid-state adhesive
solution coating, and preferably, a thermocompression process may
be used.
Pressure, temperature and time of the thermocompression process
vary depending on the type of the adhesive layer used, however, the
thermocompression process may be carried out at a temperature
selected from a range of, for example, 60.degree. C. to 150.degree.
C., and a pressure may be applied as necessary.
In one embodiment of the present application, the temporary
lamination of the first and the second adhesive layers on both
surfaces of the adhesion promoting layer may use a roll laminator
at a temperature of approximately 80.degree. C.
In the preparation method according to one embodiment of the
present application, the forming of a metal pattern comprises
forming a metal layer; and forming a metal pattern by patterning
the metal layer in the provided method for preparing a metal
pattern film.
In the preparation method according to one embodiment of the
present application, the forming of a metal layer may be carried
out through deposition or plating.
In the preparation method according to one embodiment of the
present application, the forming of a metal pattern by patterning
the metal layer is carried out by, after forming an etching resist
pattern on the metal layer, removing the metal layer that is not
covered by the etching resist pattern in the provided method for
preparing a metal pattern film.
The forming of an etching resist pattern on the metal layer may use
a photo process or a printing process, but is not limited
thereto.
After forming a metal pattern by selectively etching the etching
resist pattern-formed metal layer in the preparation method
according to one embodiment of the present application, removing
the etching resist remaining on the top of the metal pattern using
a peeling liquid may be further included.
As the peeling liquid for removing the etching resist, an alkali
solution or an organic solvent may be used.
As the alkali solution, an aqueous sodium hydroxide solution
diluted to a concentration of 1.0 wt % or greater, or potassium
hydroxide may be used, and the alkali solution is not limited
thereto as long as it is an alkali solution.
As the organic solvent, ethanol, isopropyl alcohol or acetone may
be used, and the organic solvent is not limited thereto as long as
it is an organic solvent.
FIG. 3 is a diagram illustrating a process of forming a metal
pattern on the adhesion promoting layer-formed substrate.
Specifically, it is a diagram illustrating a process of forming a
metal pattern by, after forming first and second adhesion promoting
layers on a substrate and then forming a metal layer on the first
adhesion promoting layer, forming an etching resist pattern and
then selectively etching the result.
In the preparation method according to one embodiment of the
present application, a method for preparing a metal pattern film
further comprising a process of peeling the first adhesive layer
from the metal pattern-provided substrate is provided.
FIG. 2 illustrates a peel-off process of the metal pattern film
according to the present disclosure. Specifically, it is a process
of peeling the first and the second adhesive layers from the metal
pattern-provided substrate, and illustrates a process of peeling
off the adhesive layer and the pattern film using physical
force.
When laminating the first adhesive layer on the substrate, defects
such as bubble generation, alien substance introduction or
substrate wrinkling may occur, and the peel-off process may be
progressed in order to reuse the first adhesive layer or the metal
pattern-provided substrate, and herein, by using the first and the
second adhesion promoting layers, advantages of resources recycling
and production cost reduction are obtained by preventing a
stick-slip phenomenon and thereby preventing damages on the first
adhesive layer and the metal pattern substrate.
By using the adhesion promoting layer according to one embodiment
of the present application in the process of peeling off the first
adhesive layer and the metal pattern-provided substrate, a metal
pattern film with a significantly reduced stick-slip phenomenon may
be prepared.
FIG. 1 illustrates a lamination structure of the metal pattern
film. A method of forming a conductive heating pattern on a
substrate and forming an adhesive layer has been used in the art,
however, according to the present disclosure, a stick-slip
phenomenon may be significantly reduced by further comprising an
adhesion promoting layer on a substrate.
Hereinafter, examples of the present disclosure will be described
in detail so that those skilled in the art may readily implement
the present disclosure. However, the present disclosure may be
embodied in various different forms, and is not limited to the
examples described herein.
Examples and comparative examples of a metal pattern film according
to one embodiment of the present disclosure are described in the
following Table 1.
Example 1
On polyethylene terephthalate (PET) having a thickness of 50 .mu.m,
16 nm ITO was deposited on the PET as an adhesion promoting layer
through a vapor deposition process using e-beam sputter equipment.
After that, a Cu layer was formed on the ITO layer through plating,
and then an etching resist pattern was formed through a printing
process. After forming a metal pattern by selectively etching the
etching resist pattern-formed metal layer, the etching resist
remaining on the top of the metal pattern was removed using an
aqueous sodium hydroxide solution with a concentration of 1.0 wt %.
After that, PVB was laminated as an adhesive layer for 30 minutes
under vacuum at 140.degree. C. to prepare a metal pattern film.
Examples 2 to 4
Metal pattern films of Examples 2 to 4 were prepared in the same
manner as in Example 1 except that materials of the following Table
1 were each used as the adhesion promoting layer.
Comparative Examples 1 to 13
Metal pattern films of Comparative Examples 1 to 13 were prepared
in the same manner as in Example 1 except that PET films supplied
from film manufacturers described in the following Table 1 were
each used instead of polyethylene terephthalate (PET), and the
adhesion promoting layer was not used. The substrates of the
following Table 1 are grade names of PET films supplied from
various film manufacturers.
TABLE-US-00001 TABLE 1 Adhesion Avg. 90 Max. 90 PET Promoting Peel
Peel Manufacturer Layer Thickness Strength Strength Stick/ (Grade
Name) (nm) (.mu.m) (N/cm) (N/cm) Slip Example 1 Toray ITO (16) 50
15.30 >20 X (XG7PH2) Example 2 Toray SiO.sub.2 (12) 50 >20
>20 X (XG7PH2) Example 3 Toray Al.sub.2O.sub.3 (8) 50 17.95
>20 X (XG7PH2) Example 4 Toray NbOx (5) 50 >20 >20 X
(XG7PH2) Comparative SKC (TH34) X 20 2.45 7.1 .largecircle. Example
1 Comparative Teijin X 50 0.80 2.87 .largecircle. Example 2 DuPont
(KEL86W) Comparative Teijin X 38 0.25 0.53 .largecircle. Example 3
DuPont (HPE) Comparative Teijin X 38 0.16 0.25 .largecircle.
Example 4 DuPont (G2P2) Comparative Teijin X 38 1.30 5.36
.largecircle. Example 5 DuPont (G2PZ) Comparative Mitsubishi X 188
0.95 11.8 .largecircle. Example 6 (O300E188W53B2) Comparative
Mitsubishi X 50 0.58 3.6 .largecircle. Example 7 (T604E50E92)
Comparative Mitsubishi X 50 2.30 6.8 .largecircle. Example 8
(1604E50M12) Comparative Toray X 75 3.79 18.0 .largecircle. Example
9 (XD592) Comparative Toray (U48) X 50 2.62 13.0 .largecircle.
Example 10 Comparative Toray X 50 4.15 15.41 .largecircle. Example
(XG7PH2) 11 Comparative LGC Primer X 50 4.07 15.04 .largecircle.
Example Coating PET 12 (Front Surface) Comparative LGC Primer X 50
1.90 5.27 .largecircle. Example Coating PET 13 (Rear Surface)
In Table 1, it was identified that, depending on the presence of
the adhesion promoting layer according to the present disclosure,
Examples 1 to 4 thermocompressing inorganic oxide-deposited PET and
PVB had no stick/slip phenomenon compared to Comparative Examples 1
to 13 without inorganic oxide layer deposition based on the
peel-off evaluation results.
The occurring of stick/slip phenomenon is determined from visual
observation and the shape of a peel strength-measuring graph.
In the method for measuring peel strength between the substrates in
Table 1, average force according to a 90 degree peel strength test,
a method measuring force for peeling off at a constant rate while
maintaining an adhered surface and a peeled surface to be vertical,
was expressed as Avg. 90 peel strength (N/cm), and the maximum
value was expressed as Max. 90 peel strength (N/cm). The
measurement values of the peel strength test are data capable of
identifying adhesiveness between the substrate and the first
adhesive layer and an effect of preventing a stick/slip phenomenon,
and a texture analyzer (TA XT Plus) was used as a measuring
device.
In Table 1, it was identified that, in Examples 1 to 4, average
force and maximum values for peeling off the first adhesive layer
from the metal pattern-provided substrate all increased compared to
Comparative Examples 1 to 13 without inorganic oxide layer
deposition.
Through such values, it was identified that, by using the adhesion
promoting layer of the present disclosure, adhesiveness between the
first adhesive layer and the substrate increased.
FIG. 4 is a graph measuring peel strength of the metal pattern film
according to one embodiment of the present application.
Specifically, ITO was used as the adhesion promoting layer as in
Example 1, and FIG. 4 is a graph measuring peel strength obtained
therefrom. It was identified that the graph shape was more gradual
compared to when the adhesion promoting layer was not used, which
indicates no occurrences of stick/slip phenomenon, and it was
identified that, through the strength of peel strength,
adhesiveness also increased.
From the following Table 2, damages on the metal pattern film when
using various types of acids on the metal pattern film of the
present disclosure may be identified when using NbOx (5 nm)/PET
(100 .mu.m) as the adhesion promoting layer and the adhesive layer
of the metal pattern film. As seen from the following Table 2, it
was identified that various types of acids caused no damages on the
NbOx layer and a stick/slip phenomenon still did not occur.
TABLE-US-00002 TABLE 2 Avg. 90 Peel Strength Max. 90 Peel (N/cm)
Strength (N/cm) Stick/Slip Chemical >20 >20 X Treatment X
Blending >20 >20 X acid of phosphoric acid, Nitric acid and
Acetic acid Sulfuric >20 >20 X Acid Hydrogen Peroxide Iron
>20 >20 X Chloride Client 6.12 7.13 X Company PET
In the following Table 3, it was identified that, although adhesive
strength between a metal layer and a substrate is generally
maintained by forming 20 nm or more of NiCr at the bottom of the
metal layer since adhesive strength between metal layer-substrate
decreases when electroplating on a metal seed film formed without
an adhesion promoting layer due to an increase in the cohesiveness
of the metal layer, adhesive strength between metal layer-substrate
increased after plating when introducing an adhesion promoting
layer such as NbOx, and particularly, optical properties were most
superior when using Nb.sub.2Ox alone.
A cross-cut test was used as a method of simply measuring
adhesiveness between the substrate and the thin film formed on the
substrate. This is a method of evaluating adhesiveness between
substrates by forming 100 cells through making cuts 10 times
vertically and horizontally at 1 mm intervals, and checking how
much remains on the substrate when attaching and removing an
adhesive tape (generally using ichiban tape) on the thin film.
95% to 100% of the thin film remaining based on the measurement is
expressed as 5 B, and as the degree of maintaining the thin film on
the substrate decreases, the expressed number decreases (4 B to 0
B), and this means adhesiveness decreasing. In the following Table
3, it was described as OK (5 B) for the results checked as
approximately 5 B in the cross-cut test between the plated metal
layer and the substrate.
As seen from the following Table 3, it was identified that adhesive
strength between metal layer-film was not favorable (NG) after
plating when an interlayer was not used, and adhesive strength
between film-PVB was not favorable (NG) as well after removing the
plating layer. It was identified that adhesive strength was
improved when using an inorganic oxide interlayer, an alloy
interlayer and an alloy+inorganic oxide interlayer.
In the following Table 3, sheet resistance was measured using a
contact-type sheet resistance measuring device (4-point probe), and
transmittance was measured using a COH-400 transmittance measuring
device (D65/10).
TABLE-US-00003 TABLE 3 Inorganic Alloy + Inorganic Interlayer Oxide
Alloy Oxide Category Use X Interlayer Interlayer Interlayer Metal
Deposited PET/Cu PET/Nb.sub.2Ox/ PET/NiCr/ PET/NiCr/ Film Structure
Cu Cu Nb.sub.2Ox/Cu Before Sheet 0.2 0.2 0.2 0.2 Plating Resistance
(.OMEGA./.quadrature.) Adhesive OK (5B) OK (5B) OK (5B) OK (5B)
Strength between Metal Layer- Film After Sheet 0.01 0.01 0.01 0.01
Plating Resistance (.OMEGA./.quadrature.) Adhesive NG OK (5B) OK
(5B) OK (5B) Strength between Metal Layer- Film After Transmittance
90.01 88.37 86.82 83.75 Removing (%) Scattering 1.09 1.55 1.12 1.21
Degree (%) Plating Film-PVB NG (~4 N/cm) OK (>20 N/cm) OK (~15
N/cm) OK (>20 N/cm) Layer Adhesive Strength (90 Degree Peel
Test)
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